JP2015531015A - Improved glass fiber reinforced composite - Google Patents

Abstract

Provide improved physical properties to glass fiber reinforced composites. The glass fiber reinforced composite incorporates core-shell rubber nanoparticles in the resin binder of the composite and / or in a sizing composition coated directly on individual glass fibers. [Selection figure] None

Description

  This application claims priority to US Provisional Application Nos. 61 / 679,196, filed on August 3, 2012, and 61 / 727,453, filed on November 16, 2012. Is incorporated herein in its entirety.

A conventional asphalt roofing shingle applies an asphalt coating to a glass fiber web and embeds sand or other roofing granules in the asphalt coating while still soft, and then as the asphalt hardens. Are produced by subdividing the web formed into individual singles. Glass fiber webs are usually made from glass fibers bonded together by a suitable resin binder. In addition, finely ground particulate inorganic fillers are typically included in asphalt coatings to reduce cost, improve single heat distortion resistance, and reduce asphalt UV degradation.
Co-assigned U.S. Pat.No. 7,951,240 shows that the tear strength of a roofing single produced in this way can be influenced by the type of particulate filler contained in the asphalt coating. The entire disclosure of the specification is hereby incorporated by reference. In particular, this patent shows that the tear strength of such roofing singles can be compromised when hard fillers such as dolomite, silica, slate powder, high purity magnesium carbonate are used.

Many by including core-shell rubber nanoparticles in a resin binder that is applied to the glass fiber prior to combining with the polymer that forms the matrix or body of the composite, eg, a glass fiber mat for use in making a single It has been found that the physical properties of a type of glass fiber reinforced polymer composite can be improved.
In addition, glass fibers comprising these core-shell rubber nanoparticles were made rather than applied to the fibers in subsequent manufacturing processes, including the core-shell rubber nanoparticles in a separate polymer binder. It has also been found to produce useful products using previously sized glass fibers that can be easily made by including core-shell rubber nanoparticles in the size applied to the as-fabric.

In some exemplary embodiments of the invention, it has been found that the physical properties of a glass fiber reinforced composite can be improved by incorporating core-shell rubber nanoparticles in the composite resin binder. .
In various exemplary embodiments of the present invention, the glass fiber reinforced composite comprises an improved roofing mat for use in making asphalt roofing singles. Some exemplary embodiments of the improved roofing mat comprise a glass fiber mat composed of a plurality of glass fibers and a resin binder that holds the individual glass fibers together, the resin binder comprising rubber core-shell nanoparticles It is.
Moreover, according to a further exemplary embodiment of the present invention, glass fibers comprising these core-shell rubber nanoparticles are included in a separate polymer binder, including core-shell rubber nanoparticles, followed by subsequent manufacture. It has been found that rather than or in addition to being applied to the fiber in the process, it can be made by including core-shell rubber nanoparticles in the size applied to the as-made fiber.
Accordingly, an exemplary embodiment of the present invention provides a glass fiber reinforced polymer composite comprising a matrix polymer and glass fibers dispersed in the matrix polymer, wherein the glass fiber surface comprises a coating of core-shell rubber nanoparticles. provide.

According to another exemplary embodiment of the present invention, glass filaments and fibers are provided for use in making glass fiber reinforced polymer composites. Glass filaments and fibers include glass filaments or fiber substrates with a coating of an aqueous size composition, the aqueous size composition including a film-forming polymer, an organosilane coupling agent, and core-shell rubber nanoparticles.
A further exemplary embodiment of the present invention also includes filling molten glass through a plurality of bushing orifices to create a molten glass stream and solidifying the molten glass stream to form individual filaments. Provides a continuous process for making fibers. Individual filaments can be coated with an initial size composition containing a lubricant, a film-forming resin, and an organosilane coupling agent, and can be combined together to form a fiber. The process can further include applying a coating of core-shell rubber nanoparticles to the fibers.
Some exemplary embodiments provide a glass fiber reinforced polymer composite comprising a plurality of individual glass fibers and a resin binder, wherein core-shell rubber nanoparticles are incorporated into the composite resin binder. The individual glass fibers can form a glass fiber mat that is held together by a resin binder. The resin binder may include 0.1-20% by weight rubber core-shell nanoparticles, or 0.5-10% by weight rubber core-shell nanoparticles, based on the total amount of resin in the binder. The average particle size of the rubber core-shell nanoparticles may be 250 nm or less. The resin binder can be formed from urea formaldehyde resin, acrylic resin or a mixture thereof.

In some exemplary embodiments, the core of the rubber core-shell nanoparticles is made from a synthetic polymer rubber selected from the group consisting of styrene / butadiene, polybutadiene, silicone rubber (siloxane), acrylic rubber, and mixtures thereof.
In another exemplary embodiment, the complex is an asphalt roofing single.
In various exemplary embodiments, improved roofing mats are provided for use in making asphalt roofing singles. The improved roofing mat may comprise a glass fiber mat composed of a plurality of glass fibers and a resin binder that holds the individual glass fibers together. The resin binder may include rubber core-shell nanoparticles. The resin binder may include 0.1 to 20% by weight of rubber core-shell nanoparticles based on the total amount of resin in the binder. The average particle size of the rubber core-shell nanoparticles may be 250 nm or less. The resin binder can be formed from urea formaldehyde resin, acrylic resin or a mixture thereof. The core of the rubber core-shell nanoparticles can be made from a synthetic polymer rubber selected from the group consisting of styrene / butadiene, polybutadiene, silicone rubber (siloxane), acrylic rubber, and mixtures thereof.

  In yet another exemplary embodiment, an improved comprising a glass fiber roofing mat comprised of a plurality of glass fibers and a resin binder that holds the individual glass fibers together and an asphalt coating covering the glass fiber roofing mat. Asphalt roofing singles are provided. The asphalt coating can include a particulate inorganic filler. The asphalt coating may further contain a roofing granule embedded therein. In some exemplary embodiments, the resin binder of the glass fiber roofing mat includes rubber core-shell nanoparticles. The resin binder may include 0.1 to 20 wt% rubber core-shell nanoparticles, or 0.5 to 10 wt% rubber core-shell nanoparticles based on the total amount of resin in the binder. The average particle size of the rubber core-shell nanoparticles may be 250 nm or less. The resin binder can be formed from urea formaldehyde resin, acrylic resin or a mixture thereof. The core of the rubber core-shell nanoparticles can be made from a synthetic polymer rubber selected from the group consisting of styrene / butadiene, polybutadiene, silicone rubber (siloxane), acrylic rubber, and mixtures thereof. The asphalt coating may include 30 to 80% by weight of a particulate inorganic filler selected from the group consisting of dolomite, silica, slate powder and high purity magnesium carbonate, based on the total weight of the filled asphalt. Good.

In various exemplary embodiments, a glass fiber reinforced polymer composite comprising a matrix polymer and glass fibers dispersed in the matrix polymer is provided. The surface of the glass fiber may be provided with a coating of core-shell rubber nanoparticles. In another exemplary embodiment, the surface of the glass fiber is provided with a coating comprising a mixture of core-shell rubber nanoparticles and film-forming polymer. In another exemplary embodiment, the surface of the glass fiber comprises a first coating of an initial size composition applied to the fiber during fiber manufacture, the initial size composition comprising core-shell rubber nanoparticles, film formation Contains a polymer and an organosilane coupling agent. The initial size composition may contain a hydrocarbon wax.
In some exemplary embodiments, the glass fibers are made by combining a plurality of thin glass filaments together to form individual fibers, and the individual glass after applying the initial size composition to the individual glass filaments. The filaments are matched.
In some exemplary embodiments, a second coating of a second initial size composition is applied to the fiber during fiber manufacture after combining the individual glass filaments, and a second initial size composition is added. Core-shell rubber nanoparticles and a film-forming polymer.

Glass fibers can be made by combining multiple thin glass filaments together to form individual fibers, where the surface of the glass fibers is the first size composition applied to the individual glass filaments. After providing the coating of 1, the individual glass filaments are combined, the initial size composition includes a film-forming polymer and an organosilane coupling agent, and furthermore, the surface of the glass fiber is after combining the individual glass filaments. A second coating of a second initial size composition applied to the fiber during fiber manufacture, the second initial size composition comprising core-shell rubber nanoparticles and a film-forming polymer.
The average particle size of the core-shell rubber nanoparticles may be 250 nm or less. The core of the rubber core-shell nanoparticles can be made from a synthetic polymer rubber selected from the group consisting of styrene / butadiene, polybutadiene, silicone rubber (siloxane), acrylic rubber, and mixtures thereof.
In some exemplary embodiments, the core-shell rubber nanoparticles are applied to the reinforcing glass fibers in the form of a mixture of core-shell rubber nanoparticles and film-forming resin, and further the mixture includes Based on the total amount of the film-forming resin, 0.1 to 20% by mass of rubber core-shell nanoparticles and 0.5 to 10% by mass of rubber core-shell nanoparticles are included.

In some exemplary embodiments, the glass fiber reinforced polymer composite is a roofing single.
In some exemplary embodiments, glass filaments are provided for use in making glass fiber reinforced polymer composites. The glass filament may include a glass filament substrate with a coating of an initial size composition, the initial size composition including a film-forming polymer, an organosilane coupling agent, and core-shell rubber nanoparticles.
In another exemplary embodiment, glass fibers are provided for use in making glass fiber reinforced polymer composites. The glass fiber may comprise a glass fiber substrate with a coating comprising a film-forming polymer and core-shell rubber nanoparticles.
The glass fiber may be composed of a plurality of glass filaments that are combined together, the surface of the glass filament comprising a first coating of an initial size composition that is applied to the filaments prior to combining, the initial size composition being It includes a film-forming polymer, an organosilane coupling agent and core-shell rubber nanoparticles.
The surface of the glass fiber comprises a second coating of a second initial size composition applied to the fiber after combining the filaments forming the fiber, the second initial size composition comprising additional core-shell rubber nano Contains particles and film-forming polymer.

In another exemplary embodiment, the glass fiber is made by combining together a plurality of thin glass filaments to form a fiber, wherein the surface of the glass fiber is applied to the individual glass filaments before combining. A first coating of an initial size composition, wherein the initial size composition includes a film-forming polymer and an organosilane coupling agent. The surface of the glass fiber further comprises a second coating of a second initial size composition applied to the fiber after the individual glass filaments have been combined, the second initial size composition comprising a film-forming polymer and a core -Contains shell rubber nanoparticles.
The average particle size of the core-shell rubber nanoparticles may be 250 nm or less. Further, the core of the rubber core-shell nanoparticles can be made from a synthetic polymer rubber selected from the group consisting of styrene / butadiene, polybutadiene, silicone rubber (siloxane), acrylic rubber, and mixtures thereof.
The core-shell rubber nanoparticles may be applied to the glass filaments or glass fibers in the form of a mixture of core-shell rubber nanoparticles and film-forming resin, and the mixture further comprises the total amount of film-forming resin in the mixture. Based on 0.1 to 20% by weight of core-shell rubber nanoparticles.

In yet another exemplary embodiment, molten glass is filled through a plurality of orifices in a bushing to produce a molten glass stream, solidifying the molten glass stream to form individual filaments, and lubricating individual filaments A continuous process is provided for making glass fibers comprising coating an initial size composition containing an agent, a film-forming resin and an organosilane coupling agent and combining the individual filaments together to form the fibers. . The process can further include applying a coating of core-shell rubber nanoparticles to the fibers.
The core-shell rubber particles can be applied to the glass fiber by including the core-shell rubber particles in the initial size composition.
In some exemplary embodiments, the core-shell rubber particles are formed on the glass fibers by coating the glass fibers after they are formed with a second initial size composition comprising core-shell rubber nanoparticles and a film-forming polymer. Applied. The initial size may contain core-shell rubber nanoparticles.
The average particle size of the core-shell rubber nanoparticles may be 250 nm or less, and the core of the rubber core-shell nanoparticles is from the group consisting of styrene / butadiene, polybutadiene, silicone rubber (siloxane), acrylic rubber, and mixtures thereof. It can be made from a synthetic polymer rubber of choice.
The invention can be better understood with reference to the following drawings.

FIG. 1 is a box plot of data showing the tensile strength of two types of glass fiber mats. FIG. 2 is a box plot of data showing the tear strength of two types of glass fiber mats. FIG. 3 is a box plot of data showing the tensile strength of two types of asphalt roofing singles. FIG. 4 is a bar graph showing the effect of core-shell rubber nanoparticles of the present invention on the burst strength of a high pressure composite pipe wrapped with glass fibers made according to the present invention. FIG. 5 is a graph showing the effect of these core-shell rubber nanoparticles on the interlaminar shear strength of the high-pressure composite pipe wrapped with the glass fiber of FIG. FIG. 6 is a graph showing the effect of these core-shell rubber nanoparticles on the tension applied to the glass fiber used to form the high-pressure composite pipe wrapped with the glass fiber of FIG. 4 during manufacture. .

Rubber Core-Shell Particles Rubber core-shell particles are a known commodity described in several patents. For example, rubber core-shell particles are disclosed in European Patent Application No. 2 053 083 A1, European Patent No. 5 830 086 B2, US Patent No. 5,002,982, and US Patent Application Publication No. 2005/0214534. , JP-A-11207848, U.S. Pat.No. 4,666,777, U.S. Pat.No. 7,919,549 and U.S. Patent Application Publication No. 2010/0273382. Has been incorporated. Generally speaking, the rubber core-shell particles are made from nanoparticles having a thermoplastic polymer shell or thermoset polymer shell and a synthetic polymer rubber such as styrene / butadiene, polybutadiene, silicone rubber (siloxane) or acrylic rubber. It consists of a core. In general, rubber core-shell particles have an average particle size of about 250 nm or less, usually 200 nm or less, 150 nm or less, or 100 nm or less, and have a fairly narrow particle size distribution. Rubber core-shell particles are commercially available from a number of different sources including Kenaka, Pasadena, Texas.

Glass Fiber Production Glass fiber typically extrudes molten glass into “bushing” holes, which causes the molten glass stream formed to solidify into filaments that are combined together into fibers or “rovings”. "Or" strand "is made by a continuous manufacturing process. The manufacturing process for this type of glass fiber is known and described in numerous patents. Examples include U.S. Pat.Nos. 3,951,631, 4,015,559, 4,309,202, 4,222,344, 4,448,911, 5,954,853, and 5,840,370. Nos. 5,955,518, the disclosures of each of which are incorporated herein in their entirety. Typically, the speed at which glass fibers are produced by such a process is on the order of 4,000 to 15,000 feet per minute (about 1,220 to 4,572 meters per minute). Therefore, the period of time during which such a glass manufacturing process exists, that is, the time that the molten glass leaves the bushing and the time when the glass fiber or strands formed in full size are packaged, stored and / or used is It is recognized that it is very short, about a fraction of a second.
The glass fibers can be made from any type of glass. Examples include A-type glass fiber, C-type glass fiber, E-type glass fiber, S-type glass fiber, ECR-type glass fiber (for example, Advantex® glass fiber commercially available from Owens Corning), Hiper-tex ^TM , wool glass fiber, and combinations thereof. Furthermore, the glass fiber mats of the present invention may include synthetic resin fibers such as those made from polyester, polyamide, aramid, or mixtures thereof. Similarly, fibers made from one or more naturally occurring materials such as cotton, jute, bamboo, ramie, bagasse, asa, coir, linen, kenaf, sisal, flax, ifhotol, and combinations thereof are also carbon. Can be included as a fiber.

Typically, an aqueous coating or “size” is applied to the glass filament after it has solidified but before it is contacted with a rotating spindle to elongate the glass filament. The size typically includes a lubricant that protects the fiber from damage due to wear, a film-forming resin that helps bond the fiber to the polymer that forms the body or matrix of the composite in which the fiber is used, and the film-forming resin. And an organosilane coupling agent that improves adhesion of the matrix polymer to the glass fiber surface. The size can be applied by spraying, but is typically applied by passing the filament over a pad or roller containing the size on the surface.
The sized glass fibers made in this way are used in the manufacture of a variety of different glass fiber reinforced polymer composites. In many of these manufacturing processes, the sized glass fibers are combined with the matrix polymer that forms the body or matrix of the composite, and then the glass fibers are placed in the final form of the product to be made. In another method, the sized glass fibers are first collected in a “preform” and then impregnated into a matrix resin that forms the body of the composite. This is the method used for the production of roofing singles, where the glass fibers are formed into a self-supporting web (preform), the web so made is coated with asphalt and then solidified to the final asphalt Form a single product.

The glass fiber preforms used in this method typically have individual sized glass fibers interacted with each other when subjected to the stresses and forces generated when the preform is treated and / or impregnated with a matrix resin. It is self-supporting or at least in close contact with the sense that it does not separate. For this purpose, the sized glass fibers are usually coated with an additional film-forming resin to bond the fibers together. For convenience, the coating composition used for this purpose is described herein as “binder size”. It is understood that these binder sizes are different from the size composition applied to glass filaments and fibers as part of the manufacturing process, and the size composition is referred to herein as “initial size” or “initial size composition”. It is stated in.
From the foregoing, it should be clear that the process for making glass fibers and the process for using glass fibers are considered separate and different from each other in the industry. For this reason, the process steps or operations that exist during the manufacture of glass fibers are typically referred to as “in-line” steps or operations. In contrast, the process steps or operations that exist during the use of preformed glass fibers, for example during the manufacture of glass fiber reinforced polymer composites, are typically referred to as “offline” steps or operations. This terminology is used, for example, in the above-mentioned U.S. Pat.Nos. 5,840,370, 8,163,664, 7,279,059, 7,169,463, 6,896,963, and in particular, 6,846,855. It is used in the specification of the issue. The disclosure of each of these patents is incorporated herein in its entirety. This terminology is also used in the present disclosure.

Glass Fiber Reinforced Polymer Composites Various aspects of the present invention also relate to making any type of glass fiber reinforced polymer composite. Such products are well known in the industry and are often referred to as “glass fiber reinforced plastics”. Glass fiber reinforced plastics are composed of reinforcing glass fibers and a polymer resin that forms the body or “matrix” of the composite. For convenience, these polymers are sometimes described herein as “matrix polymers”. In this connection, “polymer resin” and “polymer” are used in the broadest sense as including both artificial synthetic resins and naturally occurring resin materials such as asphalt.
The glass fiber reinforced polymer composite of the present invention can be made from any type of glass fiber. Examples include A-type glass fiber, C-type glass fiber, E-type glass fiber, S-type glass fiber, ECR-type glass fiber (for example, Advantex® glass fiber commercially available from Owens Corning), Hiper-tex ^TM and combinations thereof.

The glass fiber reinforced polymer composite of the present invention can also include fibers made from materials other than glass, for example, made from synthetic resin fibers such as polyester, polyamide, aramid, and mixtures thereof. Things. Similarly, fibers made from one or more naturally occurring materials such as cotton, jute, bamboo, ramie, bagasse, asa, coia, linen, kenaf, sisal, flax, squid, and combinations thereof are also used. It can be included as carbon fiber. Similarly, the glass fiber reinforced polymer composites of the present invention can also include non-fiber fillers, examples of which include calcium carbonate, silica sand and wollastonite. Preferably, the glass fiber reinforced polymer composite of the present invention contains a combined total of up to about 5% by weight non-glass fibers and filler, based on the weight of all fibers and filler in the composite. More preferably, all or essentially all of the fibers in the glass fiber composite of the present invention are glass fibers.
Similarly, the glass fiber reinforced polymer composites of the present invention can be made from any resin binder that has been used previously or can be used in the future as a matrix polymer for making the body or matrix of a glass fiber reinforced plastic composite. it can. Examples include polyolefin, polyester, polyamide, polyacrylamide, polyimide, polyether, polyvinyl ether, polystyrene, polyoxide, polycarbonate, polysiloxane, polysulfone, polyanhydride, polyimine, epoxy, acrylic, polyvinyl ester, polyurethane, maleic resin , Urea resins, melamine resins, phenolic resins, furan resins, polymer blends, alloys and mixtures thereof. Epoxy resins are particularly preferred.

The amount of resin binder that must be included in the glass fiber reinforced polymer composite of the present invention can vary widely and any conventional amount can be used. In some exemplary embodiments, for glass fiber mats, the amount of resin binder is about 10-30% by weight, more typically about 14-25% by weight, based on the weight of the glass fiber mat as a whole. Or about 16-22 mass%.
Glass fiber reinforced polymer composites can be made by a variety of different manufacturing techniques, including simple coating and lamination processes, but most commonly are made by molding. Two different types of molding processes are commonly used, wet molding processes and composite molding processes. In the wet molding process, the glass reinforcing fibers and the matrix polymer are combined in a mold just before molding. For example, a glass fiber mat produced in accordance with the present invention can be made by a wet laid molding process, after depositing an aqueous slurry on a moving screen, coating the wet chopped glass fiber with an aqueous dispersion of a resin binder, and Dry and cure. The formed nonwoven web is a collection of individual glass filaments that are randomly dispersed and bound together by a resin binder.
As described above, the glass fiber mat of the present invention includes a resin binder for holding the fibers together. To this end, any resin binder previously used or that can be used in the future to make glass fiber mats used in the production of asphalt roofing singles can be used as the resin binder of the present invention. Examples include urea formaldehyde resin, acrylic resin, polyurethane resin, epoxy resin, polyester resin and the like. Urea formaldehyde resin and acrylic resin are preferred, and a mixture of urea formaldehyde resin and acrylic resin is even more preferred. In such a mixture, the amount of acrylic resin is preferably about 2-30% by weight, more preferably about 5-25% by weight or about 10-20% by weight urea formaldehyde resin in the binder, based on dry solids. And the amount of acrylic resin combined.

The amount of resin binder that must be included in the glass fiber mat of the present invention can vary widely, and any conventional amount can be used. Usually, the amount of resin binder is about 10-30% by weight, more typically about 14-25% by weight, or about 16-22% by weight, based on the weight of the glass fiber mat as a whole.
The physical structure of the glass fiber mat of the present invention is not critical, and any physical structure previously used to make asphalt roofing single glass fiber mats or that can be used in the future can be Can be used to make a mat. For example, nonwoven webs of glass fibers and fabrics or scrims of woven and non-woven glass fibers can be used to make the glass fiber mats of the present invention.
Most commonly, however, the glass fiber mats of the present invention are made by a wet laid process, coating wet chopped glass fibers after deposition from an aqueous slurry onto a movable screen with an aqueous dispersion of a resin binder, It is then dried and cured. The formed nonwoven web is a collection of individual glass filaments that are randomly dispersed and bound together by a resin binder.

Roofing Singles In some exemplary embodiments, the asphalt roofing singles of the present invention are produced from the glass fiber webs of the present invention using conventional manufacturing methods, as described above, i.e., molten asphalt coating compositions. Apply sand or other roofing granules in this asphalt coating while still soft, and then subdivide the web so formed into individual roofing singles as the coating asphalt hardens Manufactured by. Any manufacturing method used or that may be used in the future may be suitable for manufacturing the glass fiber mats and singles of the present invention. Any glass fiber mat previously used or that may be used in the future to produce asphalt roofing singles may be suitable for use in producing the glass fiber mats and singles of the present invention.
To this end, any asphalt coating composition that has been used previously or can be used in the future to produce asphalt roofing singles may be suitable for use as the asphalt coating in the present invention. Such asphalt coating compositions contain a substantial amount of particulate inorganic filler, as described in US Pat. No. 7,951,240 above. In addition, asphalt coating compositions can be made from a variety of different types and grades of asphalt and can include a variety of different optional ingredients such as polymer modifiers, waxes, and the like. Any of the different grades of asphalt described therein, as well as any of the different inorganic particle fillers and optional ingredients described therein may be suitable for producing the roofing single of the present invention.

In addition to these components, the asphalt coating composition used in the present invention also includes a particulate inorganic filler. For this purpose, any particulate inorganic filler known or becoming known for use in producing asphalt roofing singles can be used. For example, calcite (ground limestone), dolomite, silica, slate powder, high purity magnesium carbonate, rock powder other than ground limestone, and the like can be used. Based on the total weight of the asphalt coating, a concentration on the order of 30-80% by weight can be used, but a concentration of about 40-70% by weight or about 50-70% by weight is more typical.
As noted above, some of these particulate inorganic fillers are known to adversely affect the tear strength of these materials and manufactured asphalt roofing singles. In particular, inorganic fillers that exhibit high hardness (i.e., greater than about 3 Moh), such as dolomite, silica, slate powder, high purity magnesium carbonate, etc. are from softer inorganic fillers such as calcite (ground limestone), etc. It is known to produce asphalt singles that have less tear strength than otherwise produced singles. Therefore, it is common in the industry to use calcite or other soft inorganic particulates as the asphalt filler, at least when an asphalt single with excellent tear strength is desired. Tear strength is an important property because it reflects the ability of an attached single to be broken by strong winds or torn from the roof substrate. Since at least asphalt roofing singles and glass fiber mats are made, tear strength and tensile strength are usually not interrelated, so the same may not be true for tensile strength. Indeed, tear strength and tensile strength can even be inversely proportional in some of these products.

Core-Shell Glass Fiber Mat According to various aspects of the present invention, the problem of insufficient tear strength of conventional asphalt roofing singles is that the core-shell rubber particles are made from the glass fiber mat from which the asphalt roofing single of the present invention is produced. It has been found that it can be solved or removed by incorporation into the resin binder used to make. Therefore, according to various embodiments of the present invention, asphalt exhibiting excellent tear strength even if hard inorganic fillers such as dolomite, silica, slate powder, high purity magnesium carbonate, etc. are included in the asphalt coating composition. A roofing single can be manufactured.
When the asphalt coating composition of the present invention is applied to the glass fiber mat of the present invention, a conventional roofing granule, such as sand, is applied to the asphalt coating while still soft, for example, in a conventional manner and into it. Embedded. The asphalt coating is then cured, and the cured web so formed is then subdivided into individual roofing singles.
It has already been proposed to use latexes of these rubber core-shell nanoparticles as a binder for glass fiber mats. See, for example, the above-mentioned European Patent Application Publication No. 2 053 083 A1, European Patent No. 5 830 086 B2, and US Patent Application No. 2005/0214534. However, in such use, the glass fiber binder is composed entirely of these rubber core-shell nanoparticles. In contrast, in some exemplary embodiments of the present invention, these rubber core-shell nanoparticles are incorporated in small but appropriate amounts as additives to improve the properties of the polymer resin that forms the body of the resin binder. May be. According to some embodiments of the present invention, the amount of these rubber core-shell nanoparticles included in the resin binder of the glass fiber mat is based on the total amount of other polymer resins of the binder, i.e. of the rubber core-shell nanoparticles themselves. Excluding the mass, it is about 0.1 to 20% by mass, more typically about 0.5 to 10% by mass or about 1 to 4% by mass.

It is already known that the tensile strength of a solid polymer mass (which reflects its fracture toughness, peel strength and lap shear strength) can be increased as a filler by including these rubber core-shell nanoparticles in the mass. Yes. However, as indicated above, tear strength and tensile strength are not interrelated in the field of asphalt roofing singles. This is illustrated in FIGS. 1 and 2, and the box plot shows the tensile strength and tear strength of glass fiber mats made with different conventional binders. See also Figure 3 which is a similar box plot showing the tear strength of asphalt roofing singles made with these different glass fiber mats. As shown in FIG. 1, the tensile strength of the mat made of binder A was better than the tensile strength of the mat made of binder B. In contrast, the tear strength of the mat made of binder A (Fig. 2) and the tear strength of the asphalt single made of binder A (Fig. 3) are both from the tear strength of the mat made of binder B and the single It was bad. This indicates that there is no direct correlation between the tear strength and tensile strength of asphalt roofing singles and related glass fiber mats. This proves that the improved tear strength of the mats and singles of the present invention is a phenomenon different from the improved tensile strength shown in the prior art.
As long as the shell of the rubber core-shell nanoparticles used in the present invention is compatible with the polymer used to form the resin binder of the glass fiber mat used in the present invention, the shell of the rubber core-shell nanoparticles used in the present invention is essential. It can be formed from any thermoplastic polymer or thermosetting polymer. “Compatible” also means that the shell-forming polymer adversely affects the physical or chemical stability of the polymer or produces an unpleasant or unnecessary by-product, which is disadvantageous to the resin binder. Means no reaction.

Additional Glass Fiber Reinforced Composite According to another exemplary embodiment, the glass fiber reinforced composite is formed by composite molding, where the glass reinforced fiber and matrix polymer are combined into a “prepreg” and then the gold Fill the mold. Such prepregs can take the form of glass fiber sheets or “veils” that are used to form self-supporting objects in which the glass fibers are randomly oriented, such as asphalt singles. In addition, prepregs are three-dimensional “skeletons” that are used to form self-supporting objects with glass fibers oriented in a predetermined direction, for example, load bearing products of complex shapes such as rocker arms for automobile suspensions. It can also take the form of Such prepregs can also take the form of pellets, pastels or aggregates composed of a matrix polymer containing randomly distributed chopped glass fibers.
Specific examples of molding processes that can be used to produce the glass fiber reinforced polymer composites of the present invention include injection molding, bladder molding, compression molding, vacuum bag molding, mandrel wrapping, wet tray up, chopper gun applications, Examples include filament winding, extrusion molding, drawing, resin transfer molding, and vacuum assisted resin transfer molding.

  According to some exemplary embodiments, glass fiber reinforced polymer composites include pressure resistant containers such as pipes (tubes) and tanks formed by filament winding or mandrel wrapping, especially matrix polymers made of epoxy resin. This type of product is included. Such products are well known and are described, for example, in the aforementioned US Pat. Nos. 5,840,370 and 7,169,463. As described in these patents, containers that can withstand such pressures typically contain some or all of the matrix polymer required to form the container around a steel mandrel that rotates in a particular direction. Made by wrapping impregnated continuous glass fiber. Then additional optional matrix polymer is added, then the matrix polymer is cured and the mandrel is removed, thereby obtaining a product container. Alternatively, such a product can be wound around a stationary steel mandrel with a preformed sheet or veil of glass fiber pre-impregnated with some or all of the matrix polymer required to form the container. It can then be prepared by adding additional matrix polymer, if necessary, curing the matrix polymer and removing the mandrels. As further described in these patents, the glass fibers used to form such products are typically binders containing a lubricant, a film-forming resin, and a coupling agent, usually an organosilane. Sized during fiber production.

According to some exemplary embodiments of the invention, the core-shell rubber nanoparticles may be incorporated into an initial size that is applied to the glass fiber as the core-shell rubber nanoparticles are made. Incorporating these nanoparticles on the fiber in this way is not only very convenient from a manufacturing standpoint, but also improved reinforcing properties when used in a variety of different glass fiber reinforced polymer composite applications. It has been found to be effective in producing glass fibers.
Generally speaking, according to the present invention, the average particle size of the core-shell rubber particles used in the present invention is less than 1/100 of the average diameter of the glass reinforcing fibers applied (i.e., less than 1%). Is desirable. Interesting are also average particle sizes of less than 1/150 (ie less than 0.67%) or less than 1/200 (ie less than 0.5%) of the glass reinforcing fibers.
As mentioned above, the tensile strength of solid polymer mass (reflecting its fracture toughness, peel strength and lap shear strength) can be increased by including these core-shell rubber nanoparticles in the mass as filler. It has been known. See “Structure-Property Relationship In Core-Shell Rubber Toughened Epoxy Nanocomposites”, Ki Tak Gam's paper submitted to the Graduate School Office at Texas A & M University in December 2003 to obtain the credits necessary for the doctoral degree. . However, as detailed above, the tear strength of asphalt roofing single and its tensile strength are not interrelated. This demonstrates that the improved tear strength of asphalt roofing singles made in accordance with the present invention is a phenomenon that differs from the improved tensile strength shown in the prior art.

In this regard, it should be appreciated that the tensile strength of a solid polymer mass is understood to be a function of its binding force, i.e., the ability to hold itself together when the mass is under tensile loading. . In contrast, the tear strength of asphalt roofing singles is a completely different phenomenon, i.e. between the veil of the binder size composition covering the glass fiber veil and the subsequently applied asphalt coating (matrix polymer). It is understood to be a function of the ability to promote adhesion. Furthermore, when core-shell rubber particles are used to improve the tensile strength of the solid polymer mass, a sufficient amount of these nanoparticles is used to fill the entire polymer mass. In contrast, because these nanoparticles are present only on the surface of the glass fiber itself and are not distributed into the mass of matrix polymer that forms the body of the glass fiber reinforced polymer composite of the present invention, a very small amount of core-shell Rubber nanoparticles are used in the present invention.
In accordance with the present invention, the core-shell rubber nanoparticles of the present invention can be applied to the reinforcing glass fiber at any time, followed by the matrix polymer to form the body of the glass fiber reinforced polymer composite of the present invention. Thus, for example, in a separate application step as part of the manufacturing process to produce the glass fiber reinforced polymer composite of the present invention, the core-shell rubber nanoparticles are made in the binder size after being made and stored. It can be applied to reinforcing glass fibers.

Alternatively, the core-shell rubber nanoparticles can be applied to the glass fibers “in-line” during glass fiber manufacturing as part of the glass fiber manufacturing process itself. Usually this means that after including these core-shell rubber nanoparticles in the initial size composition applied to the individual glass filaments used to form the glass fibers, the filaments are combined together. This is done by forming fibers. Alternatively, these core-shell rubber nanoparticles can be applied to glass fibers after they are formed in a separate aqueous size composition. For convenience, these discrete size compositions are described herein as “second initial sizes”. In the third method, both of these procedures can be used, where glass fibers are formed after some of the core-shell rubber particles have been applied to individual filaments in the initial size, and the remainder formed fibers. Applied in a second initial size later.
Regardless of which of these methods is used, in-line application allows these core-shell rubber particles to be conveniently applied during glass fiber manufacture, and continues with the glass fiber reinforced polymer composite of the present invention. The need for a separate “offline” process step during the manufacture of Furthermore, in-line application of core-shell rubber nanoparticles reduces the amount of film-forming polymer that is ultimately applied to glass fibers, at least when the nanoparticles are included in the initial size composition used during fiber manufacture. Can be made. This is because the nanoparticles must be applied with a film-forming polymer in order to promote adhesion of the core-shell rubber nanoparticles to the glass fibers. Therefore, combining these nanoparticles with the initial glass size eliminates the need for a subsequent second film-forming resin coating.

As indicated above, the core-shell rubber nanoparticles of the present invention may be applied to a glass fiber or filament substrate together with a suitable film forming resin. For this purpose, any film-forming resin previously used as a film-forming resin in glass fiber and / or filament size or that can be used in the future may be suitable for use.
As recognized in the art, choosing a resin that is compatible with the matrix resin used to make the final manufactured glass fiber composite is when choosing a film-forming resin to be used in the initial size or binder size Is the idiomatic implementation. For example, when a specific glass fiber composite is made with an epoxy resin matrix, an epoxy resin that is suitable as a film forming resin for glass fiber size is usually selected. This same conventional practice is performed in accordance with the present invention. That is, the film-forming resin used in the size containing the core-shell rubber nanoparticles of the present invention is desirably selected to be compatible with the matrix resin of the glass fiber reinforced polymer composite to be produced.
As further indicated above, because of the excellent physical properties (e.g., tensile strength) and chemical resistance of these polymers, the present invention is particularly useful for producing glass fiber reinforced polymer composites from epoxy resins. There is use. To this end, in some exemplary embodiments, it is desirable to select a medium molecular weight linear bisphenol A type epoxy resin as the film-forming resin in a size containing core-shell rubber particles. In this context, “medium molecular weight” means a weight average molecular weight of about 10,000 to 250,000. A weight average molecular weight of 15,000 to 100,000 or 20,000 to 50,000 is preferred. Linear bisphenol A type epoxies are desirable because many glass fiber reinforced polymer composites, and particularly those that require high strength and good chemical resistance, are made from linear bisphenol A type epoxy matrix resins. Epoxy resins are desirable because they do not form films effectively when their molecular weight is too high, and undergo unnecessary crystallization of coating equipment when their molecular weight is too low.

In addition to the linear bisphenol A type epoxy, a modified epoxy resin can also be used. For example, epoxy novolacs can also be used.
Specific examples of commercially available epoxy resins useful as film-forming resins for use with the core-shell rubber nanoparticles of the present invention are AD-502 epoxy aqueous emulsion from AOC, Neoxil 962 / D aqueous emulsion from DSM EpiRez 5003 from Momentive and EpiRez 3511 epoxy emulsion from Momentive. In particular, a 95: 5 ratio blend of AD-502 + EpiRez 5003 is also effective.
The amount of film-forming resin that can be present in the aqueous size containing the core-shell rubber nanoparticles of the present invention can vary widely, and essentially any amount used to provide an effective coating composition. obtain. Typically, the amount of film-forming resin is about 60-90% by weight aqueous size based on dry solids (ie, excluding water). A concentration of about 65 to 85% by weight, or about 73 to 77% by weight based on the dry weight is preferred.

Size with Combined Particles As indicated above, the aqueous size containing core-shell rubber nanoparticles of the present invention can also contain a film-forming resin. While each of these components can be separately supplied and included in the aqueous size composition, in a particularly interesting embodiment of the invention, in the emulsified particles containing these components in the aqueous size composition. Combine together.
Core-shell rubber nanoparticles are commercially available in a variety of different forms. One such form is an organic emulsion of rubber nanoparticles dispersed in a net (ie, solvent free) liquid epoxy resin. Examples of these products include the Kane Ace ^™ MX series of CSR liquid epoxy emulsions available from Kaneka Belgium NV. These liquid epoxy / rubber nanoparticle emulsions are bisphenol A type liquid epoxy resin, bisphenol-F type liquid epoxy resin, epoxidized phenol novolac type liquid epoxy resin, triglycidyl p-aminophenol type liquid epoxy resin, tetraglycidylmethylenedianiline. About 25 to 40% by weight of a stable dispersion of CSR (core shell rubber nanoparticles) in a variety of different types of liquid epoxy resin systems, including type liquid epoxy resins and cycloaliphatic type liquid epoxy resins. These liquid epoxy / rubber nanoparticle emulsions have been previously used to reinforce epoxies and other matrix resins, including matrix resins used to form glass fiber reinforced polymer composites such as filament winding pipes. It is a product.

In this regard, the significant difference between the present invention for producing a glass fiber reinforced composite containing core-shell rubber nanoparticles and the prior art is that in the present invention, the core-shell rubber nanoparticles are coated on the glass reinforced fiber of the composite. It must then be remembered that these fibers are combined with the matrix resin that forms the body of the composite. This is completely different from the earlier technology in which the core-shell rubber nanoparticles are dispersed throughout the total mass of the matrix resin. Thus, the differences between the present invention and the prior art in relation to using these commercially available liquid epoxy core shell rubber nanoparticle emulsions are coated on glass fibers using these emulsions in the present invention. After forming the initial size, these fibers are combined with the matrix resin. In contrast, in earlier techniques, these emulsions are used to form the matrix resin itself.
These commercially available liquid epoxy / rubber nanoparticle emulsions already contain two main components of the initial size of the present invention, namely the core-shell rubber particles and the epoxy resin film former, so that the core-shell rubber nanoparticle of the present invention. Represents a convenient source of particles.

According to some exemplary embodiments, before these commercially available liquid epoxy / rubber nanoparticle emulsions can be used to make the initial size of the present invention, these commercially available liquid epoxy / rubber nanoparticle emulsions are converted into aqueous emulsions. Converted. This can be easily done by using conventional high shear emulsification techniques. For example, a rubber nanoparticle aqueous size composition in which the weight ratio of rubber nanoparticles to epoxy resin is 25/75 is a conventional high shear mixing of an organic emulsion containing 25% by weight rubber nanoparticles and 75% by weight liquid epoxy resin. It can be prepared by emulsifying with a surfactant suitable for the technology and conventional epoxies, such as ethylene oxide / propylene oxide block copolymers.
According to the present invention, the amount of core-shell rubber particles applied to the glass fiber or filament substrate is typically about 0.01 to 25 mass of the solids content of the aqueous size composition that the core-shell rubber particles contain. %. More generally, the amount of core-shell rubber particles is about 0.1-5%, about 0.3-2%, about 0.5-1.5%, or about 0.7-1.3% by weight of these solids. Accordingly, the rubber nanoparticle aqueous size composition of the present invention typically contains at least two different aqueous resin dispersions, one emulsified resin particle containing a combination of film-forming resin and core-shell rubber nanoparticles. One is made by combining the other emulsified resin particles containing only the film-forming resin.

Additional Components In addition to the film-forming resin, the aqueous size composition containing the core-shell rubber nanoparticles of the present invention may also contain various additional optional components.
For example, these aqueous size compositions contain about 5-30% by weight, more typically about 8-20% or about 10-15% by weight of organosilane coupling agent, based on solids content. obtain. To this end, any organosilane coupling agent previously used or can be used in the future to enhance the adhesive strength of the film-forming binder resin to the glass fiber substrate can be used in the present invention. Further, as in the case of the binder resin, the organosilane coupling agent must be selected to be compatible with the specific film forming binder resin used.
Specific examples of useful organosilane coupling agents are Silquest A-1524 ureido silane, Silquest A-1100 aminosilane, Silquest A-1387 silylated polyazamide / methanol, Momentive Y-19139 silylated polyazamide / ethanol, Silquest A -174 methacryloxysilane, Silquest A-187 epoxy silane, Silquest A-1170 trimethoxybissilane, Silquest A-11699 triethoxybissilane, all from Momentive and Silquest A1120. For use with epoxy resin film forming resins, blends of Silquest A-1387 and Silquest A-1100 as well as Silquest A-1524 are preferred.

Another component that can be included in the rubber nanoparticle-containing aqueous size composition used in the present invention is a lubricant. Examples of commercially available lubricants that are suitable for this include Katex 6760 (also known as Emery 6760) cationic lubricant, PEG400 monooleate (PEG400 MO, Emerest 2646), PEG-200 monolaurate (Emerest 2620 ), PEG400 monostearate (Emerest 2640), PEG600 monostearate (Emerest 2662). Cationic lubricants such as Katex 6760 are used in amounts of 0.001 to 2% by weight of size solids, more typically 0.2 to 1% by weight, or about 0.5% by weight. On the other hand, PEG lubricants are typically used in amounts of 0.1 to 22% by weight of the solids content, more typically about 1 to 10% by weight, or about 7% by weight.
Yet another conventional lubricant that can be included in the rubber nanoparticle-containing aqueous size composition used in the present invention is a wax. Any wax used or usable as a lubricant wax in the glass fiber aqueous sizing composition may be used as a wax in the rubber nanoparticle aqueous size composition of the present invention. Michelman Michemlube 280 wax is a good example. A concentration of about 0.1 to 10% by weight of size solids can be used, but a concentration of about 2 to 6% by weight or 4 to 5% by weight is preferred.
Yet another conventional ingredient that can be included in the rubber nanoparticle-containing aqueous size composition of the present invention is in an amount sufficient to efficiently hydrolyze silane in the presence of acetic acid, citric acid or other organic acids. Typically, in the case of Silquest A-1100, a pH of about 4-6 is required. The final size is typically in the range of pH 5 to 6.5.
Other additives such as Coatosil MP 200 multifunctional epoxy oligomers, aqueous urethane polymers such as Michelman U6-01 or Baybond PU-403 from Bayer, Witco W-296 or W-298 from Chemtura are also known in the art. It may be included in conventional amounts in the rubber nanoparticle-containing aqueous size composition of the present invention for function.

Water Content and Filling The rubber nanoparticle-containing aqueous size composition of the present invention is applied to the glass fiber and / or filament substrate in a conventional manner using conventional coating equipment. Therefore, the rubber nanoparticle-containing aqueous size composition of the present invention is formulated with a sufficient amount of water so that its rheological properties are essentially the same or at least comparable to conventional aqueous sizes. Thus, these aqueous size compositions are typically about 2-10%, more commonly 4-8% or 5-7% by weight, based on the total weight of the aqueous size composition. Contains the total solid content.
In addition, these nanoparticle-containing aqueous size compositions are also applied in conventional amounts to the glass fiber and / or filament substrate. For example, these sizing compositions typically have a LOI (loss on ignition) of the resulting sized glass fibers and filaments of about 0.2-1.5%, more typically 0.4-1.0% or 0.5-0.8. Applied in such an amount that is%. Because the concentration of core-shell rubber nanoparticles at these sizes is typically about 0.3-2%, about 0.5-1.5%, or about 0.7-1.3% by weight based on dry solids. This means that the amount of these core-shell rubber nanoparticles applied to the glass fiber and / or filament substrate as LOI is usually about 0.001 to 0.015%, more typically about 0.002 to 0.010% or It means about 0.0025 to 0.0080%.

The following examples are presented in order to more fully describe the present invention.
Example 1 and Comparative Example A
Two glass fiber mats by conventional wet laid coating process, where wet chopped glass fibers are deposited from an aqueous slurry onto a moving screen, then coated with an aqueous dispersion of resin binder, then dried and cured Was made. Resin binders applied to both webs were each prepared using a commercial acrylic latex (Rhoplex GL 720 available from Dow Chemical) and a commercial urea formaldehyde resin latex (FG 654A available from Momentive). Furthermore, the total amount of binder applied to each web is essentially the same so that the mass ratio of acrylic resin to urea formaldehyde resin in both binders is the same (15/85) based on dry solids. The amount of resin applied was chosen to be. Example 1 resin binder, based on the combined weight of urea formaldehyde and acrylic resin in the binder, 1.7% by weight of commercially available rubber core-shell nanoparticles, especially Kane Ace MX- available from Kenaka, Pasadena, Texas. 113 rubber core-shell nanoparticles were included.
Next, the glass fiber mat thus obtained was tested for tensile strength and tear strength in the cross direction or the transverse direction. Since glass fiber mats and their associated asphalt roofing singles are generally weaker in the transverse direction than in the longitudinal direction, the transverse tensile strength and tear strength provide a better indication of the overall strength of the product.
In addition to these tests, the transverse tear strength of these glass fiber mats was also quantified by a rock dusted mat performance test. In this test, each mat was first sprayed with the same amount of powdered rock, and then the tear strength was measured in the transverse direction. This test was used because it shows a good simulation of the adverse effects on glass fiber mat properties that can be attributed to particulate inorganic fillers contained in subsequently applied asphalt coatings. This rock dust mat performance test is performed three times on each sample and the average value obtained for each test is reported below.
The results obtained are shown in Table 1 below.

table 1
Tensile strength and tear strength of the glass fiber mats of Example 1 and Comparative Example A

In the above table, “BW” refers to the basis weight, which is the mass of cured mat (glass fiber plus cured binder) pounds per 100 square feet. On the other hand, “LOI” is a general measure, percent in this industry, that shows the loss on ignition and indicates the portion of the aqueous binder that was first applied to the web remaining on the web after the binder was dried and cured. The total amount of binder applied to the web after drying and curing can be determined by multiplying BW by LOI, ie, based on dry solids.
As can be seen from Table 1, the presence of rubber core-shell nanoparticles in the binder of Example 1 had essentially no effect on the tensile strength of the glass fiber mat made from this binder (the difference in Table 1 is (Within experimental error) increased the mat's tear strength in the transverse direction relative to the control glass fiber mat of Comparative Example A. In addition, Table 1 also shows that rock dusting caused a significant decrease in the tear strength of both mats, and this decrease was more pronounced for Comparative Example A. In particular, Table 1 allowed the mat of Example 1 to retain 77% of its initial tear strength, due to the presence of these rubber core-shell nanoparticles, but when both mats were rocked, The mat of Comparative Example A shows that it retained its initial tear strength by 66%.
This data shows that the addition of these rubber core-shell nanoparticles improves the tear strength of the glass fiber mat in the transverse direction, not only in the “as-made” (uncoated) state but also in the simulated use state It shows that

Example 2 and Comparative Example B
Eight additional mats were prepared, four showing the present invention and four controls for which no rubber core-shell nanoparticles were used. These mats were prepared using the same procedures and components used in Example 1 except that the amount of rubber core-shell nanoparticles contained in the binder representing the present invention was 1.85% by weight.
Each resulting glass fiber mat is then formed into an asphalt roofing single by coating the mat with an asphalt coating composition made of coated asphalt, the asphalt coating composition also being based entirely on the asphalt coating composition. 65% by mass calcite fine particle inorganic filler.
The tensile strength of each roofing single in the longitudinal direction was measured so that it was the tear strength in both the longitudinal and lateral directions of each roofing single. Furthermore, the total tear strength of each roofing single was quantified by adding the longitudinal and transverse tear strengths together. Finally, these measured tear and tensile strengths were normalized by a single mass.
The results obtained are shown in Table 2 below.

Table 2
Tensile strength and tear strength of roofing single of Example 2 and Comparative Example B

  Table 2 shows that the addition of rubber core-shell nanoparticles to the binder of the glass fiber mat used to make the asphalt roofing single gives the single essentially the same effect as the mat. In particular, Table 2 shows that asphalt singles made with these nanoparticles, like the glass fiber mat of Example 1, have a transverse tear strength over the control single made without these nanoparticles. It is markedly large. In addition, Table 2 further shows that these nanoparticles caused these single tensile strengths to be slightly reduced in the machine direction in this case rather than the transverse direction reported in Example 1 above. ing.

Example 3
In the following examples, filament-wrapped high-pressure composite pipes were manufactured by wrapping glass fibers previously impregnated with a commercially available aqueous epoxy matrix resin dispersion around a mandrel. The winding so formed was then heated to cure the epoxy matrix resin and then the mandrel was removed to obtain the final product pipe.
The glass fibers used to make each composite were made by a conventional glass fiber manufacturing process as described above, and the thin glass filaments were coated at the initial size before being mated to the fibers. Three different experiments were performed. In the first experiment showing the prior art, the initial size did not contain core-shell rubber nanoparticles. In the remaining two experiments, the initial size contained 0.5 wt% core-shell rubber nanoparticles and 1 wt% core-shell rubber nanoparticles, respectively.
The amount of initial size applied to each glass fiber is shown in Table 3 below, and the individual composition of each initial size is shown in Table 4 below.

Table 3
Size filling amount

^* 75質量%のエポキシ樹脂及び25質量%のコアシェルゴムナノ粒子を含有するKanekaのKane Ace^TM MX-125エポキシエマルジョンの水性エマルジョン Table 4
Initial size chemical composition

^* Aqueous emulsion of Kaneka's Kane Ace ^TM MX-125 epoxy emulsion containing 75% by weight epoxy resin and 25% by weight core-shell rubber nanoparticles

The composite pipe wound with the filament so obtained was subjected to two different analytical tests. First, the burst strength of the resulting product pipe was quantified. Second, the interlaminar shear strength (ILSS) of the product pipe when exposed to 500 hours of boiling water was quantified according to the NOL ring test method, accession number AD0449719, Naval Ordinance Laboratory, White Oak, Maryland. In addition to these analytical tests, the tension generated on the glass fibers used to make the pipe during the winding operation during the production of each pipe was quantified and recorded. The obtained results are shown in FIGS.
As shown in FIG. 3, the burst strength of the product pipe of the present invention was about 8-11% greater than the burst strength of the control pipe. This indicates that the core-shell rubber nanoparticles of the present invention substantially improve the mechanical properties of the glass fiber reinforced polymer composite produced according to the present invention.
On the other hand, FIG. 4 is a graph showing that the core-shell rubber nanoparticles of the present invention have essentially no adverse effect on the interlaminar strength of the product pipe of the present invention after exposure to boiling water for 500 hours. This suggests that the core-shell rubber nanoparticles of the present invention do not adversely affect the chemical resistance of the glass fiber reinforced polymer composite of the present invention in any significant manner.
Finally, FIG. 5 shows that the tension produced on the glass fiber during the winding operation used to form the composite pipe wrapped with the filament of the present invention is essentially influenced by the core-shell rubber nanoparticles of the present invention. It is a graph which shows that there was no. This indicates that the core-shell rubber nanoparticles of the present invention do not adversely affect the manufacturing process used to produce the glass fiber reinforced polymer composite of the present invention in any significant manner.

While several embodiments of the present invention have been described above, it should be recognized that many modifications can be made without departing from the spirit and scope of the present invention. For example, it is possible to combine the core-shell rubber nanoparticle technology of the present invention with other technologies for producing glass fiber reinforced polymer composites, and in some instances even desirable.
For example, the co-assigned U.S. Pat.No. 5,840,370 described above describes a method of making a glass / polymer prepreg, part of the matrix polymer that forms the final glass fiber reinforced polymer composite or All applications are applied “in-line” as part of the glass manufacturing process. The technique is based on the invention by applying the core-shell rubber nanoparticles of the first invention and subsequently impregnating the matrix polymer of the second polymer composite with the coated glass fibers so formed. Can be combined with other technologies.
All such modifications are intended to be included within the scope of the present invention and the related general concepts of the present invention, and should be limited only by the following claims.

Claims (20)

  Glass fiber reinforced polymer composite comprising a plurality of individual glass fibers and a resin binder, wherein core-shell rubber nanoparticles are incorporated into the resin binder of the composite Polymer composite.   2. The glass fiber reinforced polymer composite of claim 1, wherein the individual glass fibers form a glass fiber mat held together by a resin binder.   The glass fiber reinforced polymer composite according to claim 1, wherein the resin binder comprises 0.1 to 20% by weight of rubber core-shell nanoparticles based on the total amount of resin in the binder.   2. The glass fiber reinforced polymer composite according to claim 1, wherein the rubber core-shell nanoparticles have an average particle size of 250 nm or less.   2. The glass fiber reinforced polymer composite according to claim 1, wherein the resin binder is formed from urea formaldehyde resin, acrylic resin, or a mixture thereof.   The glass fiber reinforced fiberglass of claim 1, wherein the core of the rubber core-shell nanoparticles is made from a synthetic polymer rubber selected from the group consisting of styrene / butadiene, polybutadiene, silicone rubber (siloxane), acrylic rubber, and mixtures thereof. Polymer composite.   2. The glass fiber reinforced polymer composite according to claim 1, wherein the composite is an asphalt roofing single.   An improved roofing mat for use in making asphalt roofing singles, wherein the improved roofing mat comprises a plurality of glass fibers and a resin binder that holds the individual glass fibers together A roofing mat comprising a mat, wherein the resin binder comprises rubber core-shell nanoparticles.   9. The roofing mat of claim 8, wherein the resin binder comprises 0.1 to 20% by weight of rubber core-shell nanoparticles based on the total amount of resin in the binder.   9. The roofing mat according to claim 8, wherein the resin binder is formed from urea formaldehyde resin, acrylic resin, or a mixture thereof.   9. The roofing mat of claim 8, wherein the core of the rubber core-shell nanoparticles is made from a synthetic polymer rubber selected from the group consisting of styrene / butadiene, polybutadiene, silicone rubber (siloxane), acrylic rubber, and mixtures thereof.   An improved asphalt roofing single comprising a glass fiber roofing mat composed of a plurality of glass fibers and a resin binder that holds the individual glass fibers together, with the glass fiber roofing mat covered by the asphalt coating, An asphalt comprising: a particulate inorganic filler therein; and an asphalt coating further comprising a roofing granule embedded therein; and the resin binder of the glass fiber roofing mat includes rubber core-shell nanoparticles. Roofing single.   13. The asphalt roofing single according to claim 12, wherein the resin binder comprises 0.1 to 20% by mass of rubber core-shell nanoparticles based on the total amount of resin in the binder.   13. The asphalt roofing single according to claim 12, wherein the resin binder is formed from urea formaldehyde resin, acrylic resin or a mixture thereof.   The asphalt roofing single according to claim 12, wherein the core of the rubber core-shell nanoparticles is made from a synthetic polymer rubber selected from the group consisting of styrene / butadiene, polybutadiene, silicone rubber (siloxane), acrylic rubber and mixtures thereof. .   The asphalt coating comprises 30 to 80% by weight, based on the total weight of filled asphalt, of particulate inorganic filler selected from the group consisting of dolomite, silica, slate powder and high purity magnesium carbonate. Asphalt roofing single listed.   A glass fiber reinforced polymer composite comprising a matrix polymer and glass fibers dispersed in the matrix polymer, wherein the glass fiber surface is provided with a coating of core-shell rubber nanoparticles. Polymer composite.   18. The glass fiber reinforced polymer composite of claim 17, wherein the surface of the glass fiber comprises a coating comprising a mixture of core-shell rubber nanoparticles and film-forming polymer.   Glass fibers are made by combining multiple thin glass filaments together to form individual fibers, and further applying an initial size composition to the individual glass filaments before combining the individual glass filaments. 18. The glass fiber reinforced polymer composite according to claim 17.   The surface of the glass fiber comprises a second coating of a second initial size composition that is applied to the fiber during fiber manufacture after combining the individual glass filaments, the second initial size composition being an additional The glass fiber reinforced polymer composite of claim 17 comprising core-shell rubber nanoparticles and a film-forming polymer.

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